Unsaturated aliphatic phosphonamides



Patented Nov. 13, 1951 2,574,516

UNSATURATED ALIPHATIC PHOSPHONAMIDES George E. Walter, Baltimore, Irwin Hornstein,

East River-dale. and George'M. Steinberg, Baltimore, Md, assisnors to The Glen L. Martin Company, Middle River, Md., a corporation oi. Maryland No Drawing. Application November 26, 1948,

Serial No. 62,234

6 Claims. (El. 260-481) phosphate, N-allyl diallyl phosphonamide, N-diallyl diallyl phosphonamide, N-N' ethylene bis cally, the invention relates to unsaturated alidiallyl amido phosphate, and dipropargyl phosphaticphosphonamide derivatives as new comphonamide. These compounds can be prepared positions of matter. These compounds are proin two ways; one consists in preparing the monoposed for use in a variety of fields, for example. chloro phosphate, e. g., for use as flamepmoiing agents, plasticizers. o waterproofing agents, coatings, lubricating 011 II modifiers, hydraulic fluid modifiers, corrosion in- (R) P cl hibigors, insecticides, fungicides, and many 10 and converting this to the amide using ammonia, others. or a primary or secondary amine. The other It is an object of this invention to prepare unmefihod consists in Preparing t dialkene D 10 saturated aliphatic phosphonamide derivatives. P111198 It is a further object of this invention to pre- (R0)1=P0H Pare composmons of matter containing 1,1105 and converting thistothe amide. using ammonia, PhPms and mtl'ogen in the molecule the nitrogen or a primary or secondary amine in the presence bemg present as a substituted or unsubstituted of carbon tetrachloride.

This invention relates to new compositions of matter and to their production. More specifiphosphonamide- The following examples illustrate suitable ways Other and further objects of this invention for preparing the unsaturated aliphatic Phos- W111 be apparent to 1311956 skmed m the phonamide derivatives of our invention.

The new compositions of matter contemplated by this invention are those unsaturated aliphatic EXAMPLE I phosphonamide derivatives having the following Preparation of diallyl phosphonamide mrmula: 1 OCHrCH=CHa 0-11. 0=P ocm-cn=cm it In a 3-neek flask provided with mechanical I agitation and external cooling are placed 116 where Ru represents an unsaturated aliphatic parts of allyl alcohol, 116 parts of toluene, and radical having from 3 to 5 carbon atoms and se- 182 parts of pyridine. Keeping the temperature lected from the class consisting of alkenyl and at -20 C. to 30 C., 153 parts of phosphorus alkynyl radicals; R1 is selected from the class oxychloride are added over a period of 3 hours. consisting of hydrogen, an alkyl radical having The temperature is raised to 0 C. and the granirom1to3 carbon atoms,anhydroxyalkyl radical ular precipitate of pyridine hydrochloride is having from 1 to 3 carbon atoms, and an unfiltered 011?. The diallyl phosphoryl chloride is saturated aliphatic radical having from 3 to 5 vacuum distilled and dissolved in toluene. Ancarbon atoms and selected from the class conhydrous ammonia gas is bubbled through the sisting of alkenyl and alkynyl radicals; and R: solution until alkaline. Ammonium chloride is is selected from the class consisting of hydrogen, filtered off, and the toluene evaporated from the an unsaturated aliphatic radical having from 3 filtrate. The residue is diallyl phosphonamide. to 5 carbon atoms and selected from the class consisting of alkenyl and alkynyl radicals, and EXAMPLE n where x represents Preparation of diallyl phosphonamide: Preparation of diallyl phosphite; its isolation and conversion to amide I L PC]; anon r 1101+ 21101 and in which m is a small whole integer and R1 (08) and Ru have the same meanings as before. 0H

Specific examples or such compounds are diallyl phosphonamide, N-methylol diallyl phos- P h ZNH: 0=P 01101; NEW! phonamide, n-n' methylene bis diallyl amide m on In a 3-neck flask equipped with dropping funnel, stirrer, and dryin tube are placed 174 parts of allyl alcohol and an equal volume of toluene. The reaction flask is cooled to 20 to -30 C. 137.5 parts of phosphorus trichloride in 70 parts of toluene are added, the rate of addition being such as to keep the temperature between -20 and 30 C. This is maintained at --20 C. for 1 hours; and dry air is passed through for another 1 /2 hours to remove hydrogen chloride. The temperature is then raised to C. To remove all of the hydrogen chloride, anhydrous ammonia is passed through, keeping the temperature at 0 C. The ammonium chloride formed is removed by filtration.

The filtrate is distilled under vacuum. Before distilling the phosphite, about .1 part of hydroquinone is added to avoid any violent polymerization on heating. The diallyl phosphite is obtained at 80 C. and 2 mm of mercury. The yield is high. 162 parts of diallyl phosphite in 154 parts of carbon tetrachloride are diluted with 350 parts of carbon tetrachloride or benzene or toluene, etc., and cooled to -15 to -20 C. Anhydrous ammonia gas is passed through with good stirring until the solution is alkaline. The precipitated ammonium chloride is filtered ofi, and the residue, vacuum distilled. Choroform and solvent are removed at room temperature; i. e., a temperature no higher than 40 C. The residue is diallyl phosphonamide having a melting point temperature of 12 to 14 C.

EXAMPLE III Direct preparation of diallyl phosphonamide To 174 parts of allyl alcohol in 400 parts of carbon tetrachloride are added at -20 to ---30 C. 137.5 parts of phosphorus trichloride in 100 parts of carbon tetrachloride. The rate of addition is such as to maintain the above temperature. The flask is kept at 20 C. for 1 /2 hours, and dry air is blown through to remove dissolved hydrogen chloride for another 1% hours. Maintaining the temperature at to 20 (7., anhydrous ammonia is passed through with vigorous stirring. This removes residual hydrogen chloride and converts the phosphite formed directly to the amide. The reaction is complete when further addition oi. ammonia does not tend to raise the temperature.

The precipitated ammonium chloride is filtered off and the flltrate vacuum distilled. Chloroform and carbon tetrachloride are removed. The residue is essentially the phosphonamide. We have found it advisable to purify the product by distillation. The amide distills at 130 C. at 2 mm. of

mercury.

EXAMPLE IV Preparation of N 'methylol diallyl phosphonamide 177 parts of the diallyl phosphonamide prepared as in Examples 1, II, or III are dissolved in 85 parts of commercial 40 per cent formaldehyde solution. The solution is allowed to stand for 48 hours at room temperature at which time the reaction is complete. Water and methanol are removed by vacuum distillation, and the residual water-insoluble oily liquid is neutralized and dried. The methylol compound cannot be crystallized even at 40 C. and is readily polymerizable.

EXAMPLEV Preparation of N-N' methylene bis diallyl amido phosphate To 207 parts of the N-methylol diallyl phosphonamide as prepared in Example IV add 177 parts of the diallyl amido phosphate. The mixture is allowed to stand for 48 hours at room temperature to insure complete reaction. The water formed is removed by vacuum distillation. The residue is a water insoluble solid material and readily polymerizable.

To 177 parts of the diallyl phosphonamide prepared as in Examples 1, II, or 131 add 15 parts of formaldehyde by using an appropriate amount of commercial 40 per cent formaldehyde solution. (The exact concentration of formaldehyde in the commercial product should be determined by analysis.) The solution is allowed to stand for 48 hours at room temperature to insure completeness of reaction. Water and methanol are removed by vacuum distillation, and the residual water insoluble solid material is dissolved in benzene and neutralized. The benzene is removed by distillation, and the solid is then dried over sulfuric acid.

EXAMPLE VI Preparation of N-allyl diallyl phosphonamide tion, and N-allyl diallyl phosphonamide is recovered by vacuum distillation. The N-allyl diallyl phosphonamide at 2 mm. of mercury boils at to C.

EXAMPLE VII.

Preparation of N-dtdllyl diallyl phosphonamide To 162 parts oi diallyl phosphite in 300 parts of carbon tetrachloride add 196 parts of diallyl amine drop-wise with stirring, keeping the temperature at about 10 to 20 C. Let stand for one to two hours with stirring. Diallyl amine hydrochloride iormed 1n the reaction is filtered off.

EXAMPLE vm Preparation of N-N' ethylene bis diallyl amido phosphate To 162 parts of diallyl phosphite in 300 parts of carbon tetrachloride add 60 parts of ethylene diamine drop-wise with stirring, keeping the temperature at about to 20 C. This is allowed to stand for one to two hours with stirring.

Ethylene diamine hydrochloride formed in the reaction is filtered off. The carbon tetrachloride is removed by distillation, and the N-N' ethylene bis diallyl amido phosphate in quantitative yield remains behind. The material is a solid, having a melting point temperature of 35 to 36 C.

EXALIPLE 1X Preparaton of dipropargyl phosphonamide O CHa-CECH O=P-O OKs-CECE At -20 C. 168 parts of propargyl alcohol are reacted with 137.5 parts of phosphorus trichloride in 500 parts of carbon tetrachloride. The phosphorus' trichloride is added drop-wise. Dry air is then blown through'the reaction mixture for 1 hours, to remove most of the hydrogen chloride formed. The temperature is maintained at 10 to 20 C.. and anhydrous ammonia is passed through, forming the amide and neutralizing the residual acid.

The propargyl phosphonamide and ammonium chloride form an insoluble layer in the carbon tetrachloride. The carbon tetrachloride layer is evaporated, leaving a small residue of the amide. The propargyl amide can be separated from ammonium chloride by heating slightly and filtering off theammonium chloride. The melting point temperature was 35 C., and the amide can be distilled at 2 mm. of mercury at 155 to 160 0.

Because of the unsaturation of these compounds, they may be readily used as monomers or comonomers for polymerization reactions. The more complex molecules, such as N-N' methylene bis amido diallyl phosphate, and particularly N-N ethylene bis amido diallyl phosphate which contain four active double bonds, will result in highly branched polymers which are suitable for a wide variety of uses.

Films produced from these polymers are much less thermoplastic and have higher softening points than polymers produced from the simpler monomer molecules.

Further, substituting an alkyl group of at least two carbon atoms for one of the hydrogen atoms on the amido group increases alkali resistance imformula o-a. 0=PO- l- B: i. .l

where Ru represents an unsaturated aliphatic radical having from 3 to-5 carbon atoms and selected from the class consisting of alkenyl and alkynyl radicals; R1 is selected from the class consisting of hydrogen, an alkyl radical having from 1 to 3 carbon atoms, an hydroxylaikyl radi-' cal having from 1 to 3 carbon atoms, and an unsaturated aliphatic radical having from 3 to 5 carbon atoms and selected from the class consisting of alkenyl and alkynyl radicals; and R2 is selected from the class consisting of hydrogen, an unsaturated aliphatic radical having from 3 to 5 carbon atoms and selected from the class consisting of alkenyl and alkynyl radicals, and X, where x represents and in which m is a small whole integer and R1 and Ru have the same meanings as before.

2; As a new composition of matter, diallyl phosphonamide having the formula 3. As a new composition of matter, N-methylol diallyl phosphonamide having the formula 4. As a new composition of matter, N-allyi diallyl phosphonamide having the formula 5. As a new composition of matter, N-diallyl diallyl phosphonamide having the formula 8. As a. new composition of matter, dipromml UNH'ID STATES PATINTB phosphonamide having the formula Number M OC-Hz-CECH 2,151,380 rum et a. Mar. 21, mo 0= 1 0cm-c cn 5 .339 Whitehfll et 11. Feb. 12, 1940 arm cns GEORGE E. WALTER. Atherton et aL: "Jour. Chem. Soc. Condom," IRWIN HORNS'I'EIN. I 194$,mes 660-683. GEORGE M. BTEINBERG. zetlchc at 8-1.: "Ber. deutlch. chem. 68-. V01.

10 Ian (1940)..4149. nEFERENcEs cum The following references are of record in the 4 the of this patent: 

2. AS A NEW COMPOSITION OF MATTER, DIALLYL PHOSPHONAMIDE HAVING THE FORMULA 